Catalyst composition for the oxidation and the oxidative dehydrogenation of olefins

ABSTRACT

This invention provides a catalyst composition for an oxidation reaction selected from the group consisting of ammoxidation of olefins to nitriles, oxidation of olefins to aldehydes and oxidative dehydrogenation of olefins (C4 - C8) to diolefins. The catalyst composition has the empirical formula: Fe10 Sb20 60 Me0.01 1 Te0.05 5 Q0.1 20 O40 177 wherein Me is V, Mo and W ; Q is Cu, Ag, Be, Mg, Ca, Sr, Ba, Zn, Cd, La, Ce and Al. The catalyst composition exhibits not only an improved catalytic activity in the reaction but also it shows desirable physical properties particularly fitted for a fluidized-bed reaction.

United States Patent n 1 Yoshino et al.

[ 1 Feb. 13,1973

[ 1 CATALYST COMPOSITION FOR THE OXIDATION AND THE OXIDATIVEDEHYDROGENATION OF OLEFINS [73] Assignee: Nitto Chemical Industry Co.,Ltd.,

Tokyo, Japan [22] Filed: Sept. 2, 1970 [21] Appl. No.: 68,879

[30] Foreign Application Priority Data Sept. 6, 1969 Japan ..44/70297[52] US. Cl. ..252/439, 252/454, 252/456, 260/465.3, 260/604 R, 260/680E Int, Cl. ..B01j 11/74 [58] Field of Search ..252/439, 456; 260/680 E,604 R, 465.3

[56] References Cited UNITED STATES PATENTS 3,338,952 8/1967 Callahan eta1 260/4653 3,409,697 11/1968 Callahan et al. 260/680 E 3,445,521 5/1969Callahan et al ..252/456 3,546,138 12/1970 Callahan et al ..252/456FOREIGN PATENTS OR APPLICATIONS 1 H1970 Yoshino et al ..260/604 R 7/1971Yoshino et al. ..260/465.3

8/1969 Germany ..242/439 Primary ExaminerDanie1 E. Wyman AssistantExaminerP. E. Konopka Att0rneyI-Ienry T. Burke, Robert Scobey, Robert S.Dunham, P. E. Henninger, Lester W. Clark, Gerald W. Griffin, Thomas F.Moran, R. Bradlee Boal, Christopher C. Dunham and John F. Scully [5 7]ABSTRACT This invention provides a catalyst composition for an oxidationreaction selected from the group consisting of ammoxidation of olefinsto nitriles, oxidation of olefins to aldehydes and oxidativedehydrogenation of olefins (C C to diolefins.

The catalyst composition has the empirical formula:

w zo-eo om-r ens-5 Qo.1-2o 40-111 wherein Me is V, Mo and W Q is Cu, Ag,Be, Mg, Ca, Sr, Ba, Zn, Cd, La, Ce and Al.

The catalyst composition exhibits not only an improved catalyticactivity. in the reaction but also it shows desirable physicalproperties particularly fitted for a fluidized-bed reaction.

4 Claims, 3 Drawing Figures CATALYST COMPOSITION FOR THE OXIDATION ANDTHE OXIDATIVE DEIIYDROGENATION OF OLEFINS BACKGROUND OF THE INVENTIONolefins, and more particularly it is concerned with multiple promotediron oxide-antimony oxide catalysts having the improved physicalproperties, said catalysts including oxides of tellurium and oxides ofat least one of metals selected from the group consisting of V, Mo and Was the promoter and also including oxides of at least one of elementsselected from the group consisting of Cu, Ag, Be, Mg, Ca, Sr. Ba, Zn,Cd, La, Ce and Al asthe modifier for improving physical properties ofthe catalysts.

The catalysts of this invention are particularly useful for thefollowing oxidation reactions and oxidative dehydrogenation reactions,and they have not only much improved catalytic activity relating to theformation of the object products but also they have desirable physicalproperties particularly fitted for commercial use.

i. Ammoxidation of olefins, such as propylene and isobutylene, to thecorresponding unsaturated nitriles, such as acrylonitrile andmethacrylonitrile, respectively;

ii. Oxidation of olefins; such as propylene and isobutylene, to thecorresponding unsaturated aldehydes, such as acrolein and methacrolein,respectively; and

iii. Oxidative dehydrogenation of olefins having from 4 to 8 carbonatoms, such as l-butene and l-pentene, to the corresponding diolefins,such as butadiene and pentadiene, respectively.

2. Description of the Prior Art US. Pat. No. 3,197,419 discloses that aniron oxideantimony oxide catalyst (hereinafter referred to as Fe' Sbsystem catalyst) is useful for the ammoxidation reaction mentioned above(i), for the oxidation reaction mentioned above (ii) and for theoxidative dehydrogenation reaction mentioned above (iii).

However, the Fe-Sb system catalyst has a drawback that it is essentiallyweak to a reductive atmosphere, and if the reaction mentioned above (i),(ii) or (iii) is carried out using the catalyst under a low oxygencontent atmosphere, it results in lowering of selectivity of the objectproduct and, in an extreme case, it results in a permanent degradationof catalysis.

Prior to the present invention, we found multiple promoted ironoxide-antimony oxide catalysts which overcome the above drawback andhave a much improved catalytic activity relating to the formation of theobject products, and we have filed a patent application relating to thereactions (i), (ii) and (iii) mentioned above using said catalysts.

The said catalyst has a composition having the following empiricalformula:

Fe,,Sb,Me,,Te Oe wherein Me represents an element selected from thegroup consisting of vanadium, molybdenum and tungsten; and a, b, c, d,and e represent atomic ratios and e the number of oxygen atoms in theoxide produced by combining the above-mentioned components whichcorresponds to 22-149.

Any catalyst which falls under the range defined by the above empiricalformula has a good activity relating to the formation of the objectproducts, and this tendency is remarkable especially when the catalysthas a Sb/Fe ratio more than 2/1. However, a catalyst having such a highcontent of antimony often produces a quantity of Sticks on its surfaceduring a high temperature calcination step which is carried out (usuallyat a temperature of 700-l ,l00C., preferably 700900C) for giving adesired activity to the catalyst. Sticks mean micro-spiny materialswhich are produced prominently on the catalyst surface. Catalystparticles, on which are present a quantity of Sticks," have anappearance like a cake sprinkled with sugar, as shown in the attachedFIG. 3. When a catalyst having Sticks is used under an operationcondition conventionally employed for the (i), (ii) or (iii) reactionaforementioned, the Sticks easily peel off from the catalyst surface andthey are scattered as minute sticky fragments to block up pipes at theexit portion of the reactor. Such a trouble may be encountered somewhatin a case using fixed bed catalyst, but remarkably in a case usingfluidized bed catalyst.

SUMMARY OF THE INVENTION According to our research, it has been foundthat Sticks consist of antimony oxides which comprise mainly antimonytetroxide, and also that from the viewpoint of anti-sticks only all ofmetal elements capable of reacting antimony oxides when said elementsare mixed with said antimony oxides and the resulting mixture iscalcined at a temperature of 300-l ,000C are useful for this purpose.These metal elements include alkali metals (Li, Na, K, Rb, Cs); 18 groupmetals (especially Cu, Ag); IIA group metals (Be, Mg, Ca, Sr, Ba); IIBgroup metals (especially Zn, Cd); IIIA group metals (especially La, Ce);IVB group metals (especially A1) of periodic Table; and polyvalentmetals selected from the group consisting of Fe, Co, Ni, Sn, U, Cr, Mn,Ti, V, Mo, W, Te, Bi, As, Th and Pb. The above-mentioned elements asmodifiers which prevent Stick formation and are effective for improvingthe physical properties of catalyst are hereinafter referred to asanti-sticks agent.

From the viewpoint of anti-sticks effect only, there are not anyspecific limitations with respect to the sort of the above-mentionedmetal elements and the formulation ratio thereof. In order to greatlydecrease or substantially extinguish Sticks without impairing theactivity of the above multiple promoted catalyst, however, there must beadded considerable limitations with respect to the sort of the metalelements and the formulation ratio thereof.

The present invention has been completed, based on the discovery of theabove-mentioned new facts, by carrying out studies on the selection ofthe sort of the metal elements as the anti-sticks" agent and on thedetermination of the amount thereof to be added, so that said metalelements achieve the expected antisticks" effect without affectingadversely on the activity of the above multiple promoted catalyst.

The present invention provides a catalyst composition for an oxidationreaction selected from the group consisting of ammoxidation of olefinsto the corresponding unsaturated nitriles, oxidation of olefins to thecorresponding unsaturated aldehydes, and oxidative dehydrogenation ofolefins having four to eight carbon atoms, to the correspondingdiolefins, said catalyst composition being free from Sticks and havingthe empirical formula:

Fe Sb Me Te Q O wherein M represents an element selected from the groupconsisting of V, Mo and W Q represents an element selected from thegroup consisting of Cu, Ag. Be, Mg, Ca, Sr. Ba, Zn, Cd, La, Ce and Al;and a, b, c, d, e

and f represent atomic ratios and b= 2O 6O c=0.0l l

f the number of oxygen atoms in the oxide produced by combining theabove-mentioned components which corresponds to 40-177.

FIG. 1 and FIG. 2 show microscopic photographs of catalyst particleswhich consist of the catalyst composition according to the presentinvention and which have no Sticks" (FIG. 1) and very few Sticks (FIG.2), respectively.

FIG. 3 shows a microscopic photograph of catalyst particles which have acomposition similar to the catalyst composition of the present inventionbut does not include any anti-sticks agent disclosed by the presentinvention and accordingly have a quantity of Sticks on their surface.From the comparison of FIGS. 1 and 2 with FIG. 3 (and from thedisclosure of examples hereinafter mentioned), the anti-sticks effect ofthe present invention will be clearly understood.

In the catalyst composition of the present invention, the antimonycomponent is added at an atomic ratio of from 20 to 60 per of the ironcomponent. In a catalyst composition including less antimony, thepossibility of Stick formation is very little even if Q" component(anti-stick component) is absent, and accordingly in this case there isno need for carrying out the anti-sticks treatment in accordance withthe present invention. On the other hand, in a catalyst compositionincluding more antimony, satisfactory antisticks" effect cannot beexpected unless excessive amount of 0 component (which might affectadversely on the catalytic activity) is added.

The above-mentioned Q component is preferably added at an atomic ratioof 0.1 to per 10 of the iron component. If a less amount of 0" componentis added, satisfactory anti-sticks" effect cannot be expected. On theother hand, if a larger amount of 0'' component is added, although theanti-sticks effect can be expected perfectly, the preferable activity ofthe base multiple promoted catalyst (Fe Sb Me Te 0,) might be affectedadversely thereby.

It is preferable to add the vanadium, molybdenum or tungsten componentat an atomic ratio of from 0.01 to 1 per 10 of the iron component. Ifmore vanadium, molybdenum or tungsten component is added, although theaction of suppressing degradation in low oxygen content i.e., thetendency of the decrease of selectivity with the decrease of the amountof residual oxygen in the gas formed remains unchanged, the absolutevalue of selectivity undesirably falls. On the other hand, if lessvanadium, molybdenum or tungsten component is added, its action ofsuppressing degradation in low oxygen content undesirably decreases.

The tellurium component is preferably added at an atomic ratio of from0.05 to 5 per 10 of the iron component. If more tellurium component isadded, the activity of the catalyst obtained is undesirably weakened,and when the catalyst is used in an atmosphere with a low oxygencontent, free-out of metallic tellurium from the resulting catalyst isundesirably observed. On the other hand, if less tellurium component isadded, the absolute value of selectivity undesirably decreases.

The catalysts having the above-mentioned composition can be produced byany known method, although it is particularly necessary that thecomponents are intimately mixed and combined. The strict chemicalstructure of a material constituting the catalyst is unknown but saidempirical formula is obtained as analytical value.

The starting material for providing the iron component of the catalystcan be selected from many members. For example, iron oxide in the formof ferrous oxide, ferric oxide or ferro-ferric oxides can be used. Also,such compounds as are finally stabilized as iron oxide after chemicaltreatment, calcining treatment or the like may be used. Those compoundsinclude iron salts of inorganic acid such as iron notrate and ironchloride, iron salts of organic acid such as iron acetate and ironoxalate, etc. The salts can be converted into oxide by neutralizing themwith a basic substance such as aqueous ammonia to form iron hydroxideand then calcining said iron hydroxide or by directly calcining thesesalts. Further, iron hydroxide or metallic iron can be used. Thematallic iron may be added in the form of fine powder or may be treatedwith heated nitric acid. In the latter case iron is converted intoferric nitrate. Whatever starting material is selected, it is importantto intimately mix the material with other components. Therefore, it ispreferably added in the form of fine powder, aqueous solution or sol.

The starting material for the antimony component may be antimony oxidesuch as, for example, antimony trioxide, antimony tetroxide or antimonypentoxide. Also, such compounds as are finally stabilized as antimonyoxide after chemical treatment, calcining treatment or the like may beused. For example, those compounds include hydrous antimony oxide,metaantimonic acid, orthoantimonic acid, pyroantimonic acid or the like.Also, hydrolyzable antimony salts such as antimony halides, for example,antimony trichloride and antimony pentachloride may be used. Theseantimony halides are hydrolyzed with water into hydrous oxides. Theantimony halides may be used as they are since they are volatile at hightemperatures.

Any one of water soluble or insoluble vanadium compounds can be used asthe vanadium component source. For example, vanadium pentoxide, ammoniummetavanadate, vanadyl oxalate, vanadium halides or the like may be used.Further, metallic vanadium can be used. It may be directly used in theform of metallic powder or may be reacted with heated nitric acid toform oxide.

Water soluble or insoluble molybdenum compounds may be used as themolybdenum component source. For example, molybdenum trioxide, molybdicacid, ammonium paramolybdate, ammonium metamolybdate, molybdenum halidesor the like may be used. Further, metallic molybdenum can be used. Itmay be directly used in the form of metallic powder or may be reactedwith heated nitric acid to form oxide.

With respect to the tungsten component source, there is applicable thesame as described concerning the molybdenum component source.

Water soluble or insoluble tellurium compounds may be used as thetellurium component source. For instance, tellurium dioxide, tellurousacid or telluric acid may be used. Further, metallic tellurium may beused. It may be directly used in the form of a metallic powder or may bereacted with heated nitric acid to form an oxide.

The starting material for providing the anti-stick component in thepresent catalyst, i.e., each component of IE, lIB, lllB, HA and 111Aabove-mentioned, may be selected from many kinds of them. The commonpreferable starting material may be nitrate, hydroxide and oxide of thecomponent.

For instance, as the starting materials of copper, cupric nitrate ormetallic copper dissolved in nitric acid may be preferably used. Also,copper hydroxide obtained by hydrolysis of cupric chloride, or cupricoxide may be used.

As the starting material of zinc and cadmium, zinc nitrate and cadmiumnitrate may be preferably used respectively. They may be used in theform of a commercial reagent or in the form of metal dissolved in nitricacid. Also, zinc chloride, cadmium chloride and hydrolysis productsthereof may be used.

As the starting material of aluninum, aluminum nitrate, or aluminumhydroxide obtained by acidhydrolysis of sodium aluminate or bybase-hydrolysis of aluminum chloride, may be preferably used.

As the starting material of beryllium, magnesium, calcium, strontium,barium, the corresponding nitrate may be preferably used. Magnesium,calcium, etc. may also be used in the form of magnesium hydroxide,magnesium oxide, calcium hydroxide, etc. dissolved in nitric acid.

As the starting material of lanthanum and cerium, the correspondingnitrate may be preferably used, but the corresponding oxide may also beused.

The activity of this catalyst system may be increased by heating at ahigh temperature. The catalyst material composition which has beenprepared to provide the desired composition and has been intimatelymixed is preferably dried, heated at a temperature of 200 to 600C. for 2to 24 hours and, if necessary, then heated at a temperature within arange of 700 to l,l00C. for l to 48 hours. The materials should beblended so that the catalyst may have a fixed composition when thecatalyst is used in the reaction after the calcining treatment.

Any other additives such as a binding agent, which serve for improvingthe physical properties of the catalyst, may be optionally added unlessthey impair the activity of the catalyst.

These additives such as a carrier, a binding agent, an extender, etc.can be optionally added irrespective of their components unless theyremarkably change the characteristics of the catalyst of the presentinvention disclosed by the above explanation or the examples mentionedbelow. The catalyst containing these additives should be also regardedas the catalyst of the present invention.

The catalyst may be used in a fixed-bed reaction in the form of pelletor may be used in a fluidized-bed reaction in the form of fine grain.However, as the trouble caused by Sticks formation is remarkableespecially in a fluidized-bed reaction, the present invention, whereinthe main advantage is to prevent Sticks formation, is more effectivelyembodied in a fluidized-bed catalyst.

The reaction conditions for the use of the catalyst of the presentinvention will be explained below.

AMMOXIDATION OF OLEFINS TO NITRILES The reactants used in theammoxidation of olefins to nitriles are oxygen, ammonia and an olefin.

The olefins should have only three carbon atoms in a straight chain, andthey are preferably selected from the group consisting of propylene andisobutylene. The olefins may be in admixture with paraffinichydrocarbons such as ethane, propane, butane and pentane.

Any oxygen source may be used, but air is usually used for economicalreasons. Air may be suitably enriched with oxygen. The molar ratio ofoxygen to olefin may be about 0.5:1 or higher, and more desirably is 1:1or higher. Suitable molar ratio is in the range of from about 2:1 toabout 6:1, particularly preferably in the range of from about 2:1 to 4:l.

The molar ratio of ammonia to olefin is suitably within the range offrom about 0.7:1 to about 3:1, but it is substantially unnecessary thatthe molar ratio is l.5:l or higher because the catalyst of the presentinvention does not decompose ammonia. The fact that ammonia is notdecomposed is advantageous in that the use of excess ammonia isunnecessary and no oxygen loss is caused by the consumption of oxygenfor the decomposition of ammonia and thereby the molar ratio of oxygento olefin can be maintained at a sufficiently high value during thereaction. This contributes to the improvement of conversion of olefinsto the corresponding unsaturated nitriles.

A hitherto known bismuth phosphomolybdate catalyst has a defect that itsammonia decomposition ability is high. According to our experimentconcerning this catalyst, it is required to suppress the decompositionof ammonia that not less than 3 mols of water per mol of olefin isadded. On the other hand, the catalyst of this invention requiressubstantially no addition of water for the same purpose. The addition ofwater is disadvantageous from thermal and operational viewpoints.

However, the addition of water is somewhat effective for suppressing theformation of carbon dioxide, and accordingly water may be added in thepresent invention, if necessary. In that case, not more than five molsof water added per mol of olefin is sufficient.

As is clear from the fact that air which is a mixture of oxygen andnitrogen can be used as the oxygen source instead of pure oxygen, anysuitable diluent may be used.

It is preferable but not always indispensable to feed an olefin, oxygen,ammonia and any optional diluent into a reactor in the form of a gaseousmixture thereof. If desired, liquefiable components may be charged inthe form of a liquid. Also, these materials may be charged separatelyinto the reactor through a few inlets. These materials, however, shouldbe in the form of a gaseous mixture when they are contacted with thecatalyst. The reaction temperature is suitably about 400 to about 550C.and reaction temperature of about 420 to 510C. gives particularly goodresults. It is preferable from operational point of view to carry outthe reaction at about atmospheric pressure, but, if necessary, thereaction may be carried out at reduced pressure or under pressure.

Space velocity is also one of the reaction conditions in a vapor phasecatalytic reaction using a solid catalyst. In the process of the presentinvention, space velocity of about 2,000 to about 100 hr? is suitableand space velocity of about 500 to about 200 hr. gives particularly goodresults. By space velocity is meant the volume (calculated in NTP) ofgas passing per unit volume of catalyst per hour.

Desired unsaturated nitrile can be recovered from the reaction productby washing the gas leaving the reactor through its exit with cold wateror a solvent which is suitable for the extraction of the nitrile. Anyother recovery process which is customarily used in this kind ofreaction may be used.

In the practice of the present invention, any one of the fixed-bed type,moving-bed type and fluidized-bed type apparatus, which are customarilyused in vapor phase catalytic reactions, can be used.

OXIDATION OF OLEFINS TO ALDEHYDES The reactants used in the oxidation ofolefins to aldehydes are oxygen and an olefin.

The olefins and the oxygen sources are the same as described above.

The molar ratio of oxygen to propylene may be about 0.5:1 or higher, andmore desirably is 1:1 or higher. Preferable molar ratio is in the rangeof from about 2:1 to about 6:1

The addition of water is somewhat effective for suppressing theformation of carbon dioxide, and water may be added in the presentinvention, if necessary. In that case, not more than mols of water addedper mol of propylene is sufficient.

The reaction temperature is suitably about 370 to about 500C. andreaction temperature of about 410 to 480C. gives particularly goodresults. It is preferable from operational point of view to carry outthe reaction at about atmospheric pressure, but, if necessary, thereaction may be carried out at reduced pressure or under pressure.

Space velocity is also one of the reaction conditions in a vapor phasecatalytic reaction using a solid catalyst. In the process of the presentinvention, space velocity of about 2,000 to about 100 hr. is suitableand space velocity of about 1,000 to about 400 hr.- gives particularlygood results. The definition of space velocity is the same as mentionedabove.

Desired unsaturated aldehyde can be recovered from the reaction productby washing the gas leaving the reactor through its exit with cold wateror a solvent which is suitable for the extraction of the aldehyde. Anyother recovery process which is customarily used in this kind ofreaction may be used.

With respect to the feeding procedures of reactants into a reactor, andthe types of the reactor, there is applicable the same as mentionedconcerning the ammoxidation except for ammonia.

OXIDATIVE DEHYDROGENATION OF OLEFINS TO DIOLEFINS The reactants used inthe oxidative dehydrogenation of olefins to diolefms are oxygen and anolefin.

By the term olefin used concerning oxidative dehydrogenation is meant anopen chain olefin having four to eight nonquaternary carbon atoms, ofwhich at least four are arranged in series in a straight chain. Theolefins include I-butene, cis-2-butene, trans-2-butene,2-methyle-I-propene, l-pentene, cis-2-pentene, trans Z-pentene,Z-methyI-I-butene, 3-methyl-l-butene, 3- methyI-Z-butene, 2-hexene,2-methyI-l-pentene, 3- methyl-l-pentene, 4-methyl-I-pentene, 2-methyl-2-pentene, 3-ethyl-l-pentene, 2-ethyl-l-hexene and the like.

According to the catalyst of this invention, the olefins can beconverted to the corresponding diolefins with an improved yield. Forinstance, there are obtained butadiene from butenes (I-butene,cis-2-butene, trans-Z-butene or mixture thereof), pentadiene from 1-pentene or Z-pentene, isoprene from Z-methyl-l-butene, and hexadienefrom l-hexene.

Recently, the oxidative dehydrogenation of butenes to butadiene is notedbecause of its commercial importance. According to this invention, asthe butene sources, there may be used not only l-butene, cis-2-butene,trans-2-butene and the mixture thereof, but also spent B-B fractionwhich is obtained from B-B fraction by removing butadiene andisobutylene therefrom, said B-B fraction being obtained in petroleumrefinery or by thermal cracking of petroleum fractions such as naphtha.In case of using said spent BB fraction, paraffins contained therein aresubstantially inert in a reaction zone according to this invention. Withrespect to isobutylene which still remains in said material as impuritynot completely removed therefrom, it is converted mainly to methacroleinin a reaction zone according to this invention. It is, however, easy toseparate the methacrolein from the object product (butadiene) byutilizing the boiling temperature difference between them and/or thesolubility difference in a solvent between them.

Any oxygen source may be used, but air is usually used for economicalreasons. Air may be suitably enriched with oxygen. The molar ratio ofoxygen to propylene is desirably 0.521 or higher. Preferable molar ratiois in the range of from about 1:1 to about 4: l.

The addition of water is somewhat effective for suppressing theformation of carbon dioxide, and water may be added in the presentinvention, if necessary. In that case, not more than 5 mols of wateradded per mol of propylene is sufficient.

The reaction temperature is suitably about 350 to about 500C. andreaction temperature of about 400 to 480C. gives particularly goodresults. It is preferable from operational point of view to carry outthe reaction at about atmospheric pressure, but, if necessary, thereaction may be carried out at reduced pressure or under pressure.

Space velocity is also one of the reaction conditions in a vapor phasecatalytic reaction using a solid catalyst. In the process of the presentinvention, space velocity of about 2,000 to about 100 hr.- is suitableand space velocity of about 500 to about 150 hr." gives particularlygood results. The definition of space velocity is the same as mentionedabove.

Desired diolefin can be recovered from the reaction product by washingthe gas leaving the reactor through its exit with a solvent such asacetonitrile which is suitable for the extraction of the diolefin. Anyother recovery process which is customarily used in this kind ofreaction may be used.

With respect to the feed procedures of reactants into a reactor, and thetypes of the reactor, there may be applicable the same as mentionedconcerning the ammoxidation except for ammonia.

The constitution and effect of the present invention are illustrated bythe following examples and comparative examples.

DESCRIPTION OF PREFERRED EMBODIMENTS Catalysts Preparations Example 1 Acatalyst having the empirical formula:

85 0.1 z ro so 124 2M) was prepared as follows:

2.43 Kilograms of metallic antimony powder (100 mesh or finer) was addedin portions to 8.86 liters of heated nitric acid (specific gravity1.38). After the whole amount of the antimony had been added and thegeneration of a brown gas had ceased, the mixture was allowed to standat room temperature for 16 hours. Excess nitric acid was then removedand the precipitate formed was washed with water. The precipitate wasthencrushedin a ball mill. H A V H r 0.223 Kilograms of electrolyticiron powder was added in portions to a mixture consisting of 1.6 litersof nitric acid (specific gravity 1.38) and 20 liters of water. Theresulting mixture is heated to be completely dissolved. (11) 4.7 gramsof ammonium metavanadate (NHNO was dissolved in 0.5 liters of waterwhile heating. (I11) 184 grams of telluric acid was dissolved in 1.5liters of water. (IV) As a carrier component 7.21 Kilograms of silicasol (Snowtex-O manufactured by Nissan Chem. Co.; SiO 20 percent byweight) was used. (v)

513 grams of magnesium nitrate [Mg(No 611 0] were dissolved in silicasol above mentioned. (Vl) (l)-(Vl) were mixed, and an aqueous ammoniasolution (15 percent) was added thereto in portions with stirring toadjust the Pl-lof the mixture to 2. The resulting mixture was heatedwith stirring at 100C. for 5 hours.

The slurry thus obtained was adjusted to a suitable concentration andspray-dried by a conventional spraydryer equipment.

Micro-spherical particles thus obtained were gradually heated to anelevated temperature in a rotary calciner having an external heatingsystem, and the final temperature was 550C. The particles were thencalcined at 820C. for 2 hours in an electric furnace having an externalheating system. Example 2 A catalyst having the empirical formula:

rz 0.1 2 m so 131 2M) was prepared in the same manner as in Example 1except that 1.16 Kilograms of cupric nitrate [Cu(NO '3H O] were usedinstead of 513 grams of magnesium nitrate. The calcination temperatureis also the same as in Example 1. Example 3 A catalyst having theempirical formula:

g0.7 0.1 z m so 120 flso was prepared in the same manner as in Example 1except that 48 grams of silver nitrate was used instead of 513 grams ofmagnesium nitrate. Example 4 A catalyst having the empirical formula:

3 0.1 a w so 122 2)so was prepared in the same manner as in Example 1except that 357 grams of zinc nitrate [Zn(NO -6H O] was used instead of513 grams of magnesium nitrate. Example 5 A catalyst having theempirical formula:

2 0.1 2 m so 122 fiso was prepared in the same manner as in Example 1except that 347 grams of cerium nitrate [Ce(NO -6H 0 was used instead of513 grams of magnesium nitrate. Example 6 A catalyst having theempirical formula:

a 0.1 2 m so 124 z)so was prepared in the same manner as in Example 1except that 450 grams of aluminum nitrate [Al(NO 911 0] was used insteadof 513 grams of magnesium nitrate. Example 7 A catalyst having theempirical formula:

2 as l w zs 12 2):: was prepared as follows:

There was taken 291 grams of antimony trioxide powder (20 p. or finer).I

There was taken 44.7 grams of electrolytic iron powder. 380 ml. ofnitric acid (specific gravity 1.38) was mixed with 400 ml. of water andthe mixture was heated. The iron powder mentioned above was added inportions into the mixture to completely dissolve. Then 10.2 grams oftellurium powder was added thereto in portions to completely dissolve.(n)

10.4 grams of ammonium tungstate was dissolved in 500 ml. of water withheating. in

69.3 grams of lanthanum nitrate [La(NO -6l-l,0] was dissolved in 500 ml.of water. w

As a carrier component 721 grams of silica sol (Snowtex-O manufacturedby Nissan Chem. Co. SiO, 20 percent by weight) was used. (v)

(l)-(V) were mixed, and an aqueous ammonia solution was added thereto inportions with stirring to adjust the PH of the mixture to 2. Theresulting mixture was heated with stirring at C for 3 hours.

The slurry thus obtained was adjusted to a suitable concentration andspray-dried by a conventional spraydryer equipment.

Micro-spherical particles thus obtained were heated at 250C. for 2 hoursand then at 450C. for 2 hours, and finally were calcined at 810C. for 5hours. Example 8 A catalyst having the empirical formula:

2 05 x m zs 12 fiao was prepared in the same manner as in Example 7except that 62.1 grams of cerium nitrate was used instead of 69.3 gramsof lanthanum nitrate.

Example 9 A catalyst having the empirical formula:

88 as l m zs 17 zho was prepared in the same manner as in Example 7except that 164 grams of magnesium nitrate was used instead of 69.3grams of lanthanum nitrate.

Example 10 A catalyst having the empirical formula:

a as 1 r0 zs 12 zho was prepared in the same manner as in Example 7except that 74 grams of cadmium nitrate [Cd(NO 411 0] was used insteadof 69.3 grams of lanthanum nitrate.

Example 11 A catalyst having the empirical formula:

a as l m zs 13 2)ao was prepared in the same manner as in Example 7except that 90 grams of aluminum nitrate [Al(NO 911 0] was used insteadof 69.3 grams of lanthanum nitrate.

Example 12-a A catalyst having the empirical formula:

ms as l 10 zs ss zho was prepared in the same manner as in Example 7except that 9.7 grams of cupric nitrate [Cu(NO -3H O] was used insteadof 69.3 grams of lanthanum nitrate. Example l2-b A catalyst having theempirical formula:

a as x m zs 12 flso was prepared in the same manner as in Example 12-aexcept that 58 grams of cupric nitrate was used. Example 12-0 A catalysthaving the empirical formula:

e as l 10 zs 7a'( 2)ao was prepared in the same manner as in Example12-a except that 174 grams of cupric nitrate was used. Example 13 Acatalyst having the empirical formula:

ms 015 l w zs 06B 2)so was prepared as follows:

There was taken 2.91 kilograms of antimony trioxide powder or finer).(1)

There was taken 0.447 kilograms of electrolytic iron powder. 3.2 litersof nitric acid (specific gravity 1.38) was mixed with 2 liters of waterand the mixture was heated. The iron powder mentioned above was added inportions into the mixture to completely dissolve. n

35.3 grams of ammonium molybdate [3(N1-l ),O-7 MoO -4H,O] was dissolvedin 500 ml. of water and then 184 grams of telluric acid was addedthereto to dissolve. (111) As a carrier component 9.61 kilograms ofsilica sol (Ludox l-lX manufactured by DuPont SiO, 30 percent by weight)was used. (IV) 97 grams of cupric nitrate [Cu(NO,),'3H,O] was dissolvedin 500 ml. of water. v

(1)-(V) were mixed, and an aqueous ammonia solution was added thereto inportions with stirring to adjust the PH of the mixture to 2.0. Theresulting mixture was heated with stirring at 100C. for 4 hours.

The slurry thus obtained was adjusted to a suitable concentration andspray-dried conventionally.

Micro-spherical particules thus obtained were heated at 250C. for 2hours and then at 400C. for 2 hours, and finally were calcined at 810C.for 4 hours. Example 14 A catalyst having the empirical formula:

2 025 l w zs 11 zko was prepared in the same manner as in Example 13except that 693 grams of lanthanum nitrate [La(NO 61-1 0] was usedinstead of 97 grams of cupric nitrate. Example 15 A catalyst having theempirical formula:

3 ms l 10 as 72 2M) was prepared in the same manner as in Example 13except that 600 grams of aluminum nitrate was used instead of 97 gramsof cupric nitrate.

Example 16 A catalyst having the empirical formula:

a 025 l 10 zs 11 2)so was prepared in the same manner as in Example 13except that 449 grams of beryllium nitrate was used instead of 97 gramsof cupric nitrate.

Example 17 A catalyst having the empirical formula:

025 l w zs 13 z)oo was prepared in the same manner as in Example 13except that 1.03 kilograms of magnesium nitrate [MgWOQZ-GH O] was usedinstead of 97 grams of A cupric nitrate. Example 18 A catalyst havingthe empirical formula:

5 015 l w 25 1a 2)so was prepared in the same manner as in Example 13except that 945 grams of calcium nitrate 05 10 4H,Oam was used insteadof 97 grams of cupric nitrate. Example 19 A catalyst having theempirical formula:

a 015 l m zs 11 2)) was prepared in the same manner as in Example 13except that 508 grams of strontium nitrate was used instead of 97 gramsof cupric nitrate. Example 20 A catalyst having the empirical formula:

a 025 l 10 zs 11 2)) was prepared in the same manner as in Example 13except that 627 grams of barium nitrate [Ba(NO,),] was used instead of97 grams of cupric nitrate. Example 21 A catalyst having the empiricalformula:

a 015 l w zs 71 an was prepared in the same manner as in Example 13except that 714 grams of zinc nitrate [Zn(NO ),'6H O] was used insteadof 97 grams of cupric nitrate. Example 22 A catalyst having theempirical formula:

s 015 l m zs n zho was prepared in the same manner as in Example 13except that 740 grams of cadmium nitrate [Cd(NO -4H O] was used insteadof 97 grams of cupric nitrate. Comparative Example 1 A catalyst havingthe empirical formula:

EVALUATION TEST OF CATALYST AND RESULTS THEREOF The evaluation testresults (the judgement of Sticks formation degree) of the catalystsproduced by the foregoing examples and the forgoing comparative examplesare shown in Tables 1-3.

1. Optical Microscopic Observation The simplest way of judging Sticksformation degree directly and sensuously is to observe a test catalystdirectly under an optical microscope. All of the test catalysts wereobserved under an optical microscope by reflection method and some ofthem were photographed (about 100 magnifications).

FIGS. 1 and 2 of the attached drawings show optical microscopicphotographs of catalysts of examples l2-c and 6 respectively, and FIG. 3shows an optical microscopic photograph of the catalyst of comparativeexample 2.

A, B and C described in Tables l-3 mean the following factsrespectively:

A. Sticks formation is substantially not or very little observed (astate which is the same as or similar to that of FIG. 1)

B. Sticks formation is a little observed, but the amount thereof is solittle that practically any hindrance is scarcely experienced (a statewhich is the same as or similar to that of FIG. 2)

C. Sticks formation is remarkably observed, and

the amount thereof is so much that practically considerable hindrance isexperienced (a state which is same as or similar to that of FIG. 3)

D. A state which is more miserable than C, and is of little value ascommodity.

2. Intensity Ratio of X-ray Diffraction for Antimony Tetroxide (Sb O Itis found that Sticks" are antimony oxides which comprise mainly antimonytetroxide, and that there are clear correspondence relations between theamount of Sticks formed (observed by an optical microscope) and theamount of antimony tetroxide in the catalyst (calculated by X-raydiffraction).

Numerical values in the column Sb,0, Intensity Ratio of X-rayDiffraction of Tables l-3, are those obtained as follows: Each of thetest catalysts was crushed to finely ground powder form, and theresulting powder was subjected conventionally to X-ray diffractionanalysis to obtain diffraction intensity of antimony tetroxide in eachcatalyst. The values thus obtained are expressed in relative valuescompared with the diffraction intensity of catalyst of comparativeexample 2 (said diffraction intensity is defined as l).

The less the amount of antimony tetroxide in a catalyst, i.e., thesmaller the diffraction intensity of antimony tetroxide in a catalyst,the lessthe amount of Sticks formed.

Compared with the fact that the judgement of Sticks formation by meansof an optical microscopic observation is sensuous and qualitative, thejudgement of Sticks formation by means of the intensity ratio of X-raydiffraction for antimony tetroxide can be said to be relativelyquantitative.

3. Deviation of Antimony Content A test catalyst (catalyst particles forfluidized-bed) was subjected to attrition test for a given time under adefinite violent fluidized state, and antimony content of the catalystbefore the test (L by weight) and antimony content of fine powderedattrition-loss catalyst which was lost by attrition and scattered out ofthe system during the test period (M by weight) were measured. From thevalues, deviation of antimony content N [N=(ML)/L X was calculated. Thevalue N shows a degree of Sticks formation considerably quantitatively.This will be easily understood from the fact that Sticks are of antimonyoxide which comprise mainly antimony tetroxide and that Sticks tend topeel off easily from the catalyst surface to be scattered (i.e., thatpeeling-off of Sticks is done much easier than attrition loss of thecatalyst per se). It is of course that the lower N value of thecatalyst, the less the amount of Sticks formed.

Deviation of antimony content in Tables l-3 shows N value thus measured.

The fiuidization condition employed in this test is based upon thecondition described in Test Method for Synthetic Cracking Catalyst 6/314m l/57 published by American Cyanamide Co., said Test Method beingknown as a test method of strength of fluidized cracking catalyst (whatis called FCC catalyst").

The tests were carried out with catalyst particles having a particlesize range of 44-88 microns, and the test time is 15 hours per onesample. Analysis of antimony content in catalyst was carried out bymeans of luminescent X-ray method.

ACTIVITY TEST OF CATALYST In order to show the fact that anti-stickscomponent (Qe) contained in the catalyst composition of the presentinvention does not affect adversely on the activity of base multiplepromoted catalyst (Fe, Sb Me, Te 0,), the following activity tests werecarried out.

a. Test using a fluidized bed reactor Into a reactor having 2 inches ofinside diameter and equipped inside thereof with baffle plates whichserves to increase the contact efficiency, there was charged 1,600 gr.of a catalyst having a mean weight particle size of 50-70 microns.Gaseous starting materials, in case of the acrylonitrile production, forexample, such as propylene, ammonia and air, were introduced thereintoat a rate of 13 cm/sec. Gaseous products were gas-chromatographed forquantitative analysis.

On each catalyst to be tested there was detected the optimum reactiontemperature at which the maximum conversion of starting hydrocarbon tothe object compound was obtained and the conversion at the temperaturewas shown in Table 4.

conversion of starting hydrocarbon to the object com- 10 example 5 poundwas obtained and the conversion at the temperature was shown in Table 4.

The term conversion in Table 4 means conversion of olefin (startinghydrocarbon) to the object product, and the definition thereof is asfollows:

conversion carbn Weight of the object compound formed carbon weight ofolefin fed TABLE 2 EVALUATION TEST OF CATALYST 2 [CATALYST COMPOSITION IFe Sb W Te, 0 1' 2)sol Test Micro- Sb,O, Deviation of scopic IntensitySb Content Catalyst Qe Observa- Ratio 0 X-ray tion Diffraction L A 3 4.6C2: A 3 3.8 9 Mg, A 0 1.5 10 Cd, A 2 2.3 1 1 Al A l 1.2 12-a Cu B 4 6.512-h Cu, A 0 1.1 l2-c Cu, A 0 0.7 Comparative None C 10 25.2 Example 2TABLE 3 EVALUATION TEST OF CATALYST (3) [CATALYST COMPOSITION Fe Sb MoTe, TABLE 1 EVALUATION TEST OF CATALYSTS (1) Q, 0," (8109 Test Micro-Sb,O Deviation of [Catalyst Composition Fe Sb. V Te Q 0, scopicIntensity Sb Comm z)so] Catalyst Qe Observa- Ratio of X-ray tionDiffraction Test Micro- Sb,O. Deviation of scopic Intensity Sb ContentCatalyst Qe Observa- Ratio 0 X-ray example 13 Cu B 3 3.9 tionDiffraction 14 La, A 1 2.1 15 Al A 1 1.4 16 Be; A 0 2.0 example 1 Mg A 44.2 17 Mg,, A 0 1.7 2 Cu A 2 1.1 18 Ca: A 0 0.9 3 ABM B C 11 18.5 19 Sr;A 0 1.3 4 Zn B 8 7.8 20 Ba, A 1 1.5 5 Ce, B 8 5.0 21 Zn;, A 0 0.8 6 Al,B 8 4.1 22 Cd; A 1 1.2 Compara- Comparative None D 17 45.0 tive None C 820.9 Example Example 1 3 TABLE 4.ACTIVITY TEST RESULTS Reactant gascomposition (molar ratio) Reaction temper- Contact Conver- StartingHydroature time sion, Reactor Test catalyst hydrocarbon carbon NH; AirH1O C.) (see) Object product percent used Example:

1 Propylene 1 1. 2 460 G Acrylonitrlle 75 a 4... Iso-butylene. 1 1. 5440 (i ltlethacrylonitrile.... b Propylene 1 450 5 Acrolein 67 b 6.do... 1 1. 2 460 6 Aerylonitr11e. 7 1 a Propylene 1 1. 2 460 6Aerylonitrile. 76 a Comparative Example 1 {Iso-bntyleno 1 1. 5 440 6Methacrylon1trlle 62 b Propylene 1 460 5 Acrolein 68 1) Example 7. 1 4007 Butadlene 78 h 10 l 450 5 Acroleln. 68 l) 1 1.2 460 6 Acrylonltrlle 77l) 1 1. 2 460 6 Acrylonitz'lle 76 h lButened... 1 400 7 Butedlene 711 hExample:

13 Propylene 1 1. 2 460 6 Aerylonltrl 1e. 77 n. 16. Iso-butylene. 1 1. 5440 f1 Mothacrylonlt 66 h 18. ..do 1 410 5 Methacroleln (,2 l; 22Butenel 400 7 Butadiene... 79 b Propylene 1 1. 2 460 6 Acrylonltrile 76a Comparative Example 3 lso-bntylene 1 410 5 Methacroleln 63 l) Buteued1 400 7 Butadlene 78 b What we claim is:

l. A catalyst composition for an oxidation reaction selected from thegroup consisting of ammoxidation of olefins to the correspondingunsaturated nitriles; oxidation of olefins to the correspondingunsaturated aldehydes, and oxidative dehydrogenation of olefins havingfour to eight carbon atoms to the corresponding diolefins, said catalystcomposition having the empirical formula:

Fe Sb Me Te Q O; wherein Me represents an element selected from thegroup consisting of V, Mo and W Q represents an element selected fromthe group consisting of Cu, Ag, Be, Mg, Ca, Sr, Ba, Zn, Cd, La, Ce andAl and a, b, c, d, and f represent atomic ratios and f the number ofoxygen atoms in the oxide produced by combining the above-mentionedcomponents which corresponds to 40 177.

2. The catalyst composition according to claim 1 wherein said catalystcomposition is supported by a silica carrier, and the carrier is presentin 10 to 90 percent by weight of the entire catalyst consisting of thecatalyst composition and the carrier.

3. The catalyst composition according to claim 1, activated by heatingat a temperature in the range of from 700 to l,l00C.

4. The catalyst composition according to claim 1, subjected to heattreatment at a temperature in the range of from 200 to 600C. for 2 to 24hours followed by calcination at a temperature in the range of from 700to l,l00C. for [-48 hours.

1. A catalyst composition for an oxidation reaction selected from thegroup consisting of ammoxidation of olefins to the correspondingunsaturated nitriles; oxidation of olefins to the correspondingunsaturated aldehydes, and oxidative dehydrogenation of olefins havingfour to eight carbon atoms to the corresponding diolefins, said catalystcomposition having the empirical formula: FeaSbbMecTedQeOf wherein Merepresents an element selected from the group consisting of V, Mo and W; Q represents an element selected from the group consisting of Cu, Ag,Be, Mg, Ca, Sr, Ba, Zn, Cd, La, Ce and Al ; and a, b, c, d, and frepresent atomic ratios and a 10 b 20 - 60 c 0.01 - 1 d 0.05 - 5 e 0.1 -20 f the number of oxygen atoms in the oxide produced by combining theabove-mentioned components which corresponds to 40 -
 177. 2. Thecatalyst composition according to claim 1 wherein said catalystcomPosition is supported by a silica carrier, and the carrier is presentin 10 to 90 percent by weight of the entire catalyst consisting of thecatalyst composition and the carrier.
 3. The catalyst compositionaccording to claim 1, activated by heating at a temperature in the rangeof from 700* to 1,100*C.